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Efficient and Practical Oxidative Bromination and Iodination of Arenes and Heteroarenes with DMSO and Hydrogen Halide: A Mild Protocol for Late-Stage Functionalization

An efficient and practical system for inexpensive bromination and iodination of arenes as well as heteroarenes by using readily available dimethyl sulfoxide (DMSO) and HX (X = Br, I) reagents is reported. This mild oxidative system demonstrates a versatile protocol for the synthesis of aryl halides. HX (X = Br, I) are employed as halogenating reagents when combined with DMSO which participates in the present chemistry as a mild and inexpensive oxidant. This oxidative system is amenable to late-stage bromination of natural products. The kilogram-scale experiment (>95% yield) shows great potential for industrial application.

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Benzothiophene – Wikipedia,
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Sensitive Assays by Nucleophile-Induced Rearrangement of Photoactivated Diarylethenes

Upon light-induced isomerization, diarylethenes (DAEs) equipped with reactive aldehyde moieties rearrange selectively in the presence of amines, accompanied by decoloration. In a comprehensive study, the probe structure was optimized with regard to its inherent reactivity in the nucleophile-triggered rearrangement reaction. Detailed structure-reactivity relationships could be derived, in particular with regard to the type of integrated (het)aryl moieties as well as the location of the formyl residue, and the probes’ intrinsic reactivity with primary and secondary amines was optimized. Utilizing an ancillary base, the initially formed rearrangement product can engage in a subsequent catalytic cycle, leading to an amplified decoloration process. This additional catalytic pathway allows us to enhance the sensitivity of our method and successfully discriminate between amines and thiols. Moreover, probes that exhibit strong analyte-induced fluorescence modulation have been designed to further decrease the detection limit by using a more sensitive read-out. The optimized DAE probes are promising molecular components for future programmable sensing materials and devices.

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Benzothiophene – Wikipedia,
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Thermally Irreversible Photochromic Systems. Reversible Photocyclization of 1,2-Bis(2-methylbenzothiophen-3-yl)perfluorocycloalkene Derivatives

1,2-Bis(2-methylbenzothiophen-3-yl)perfluorocyclopentenes undergo thermally irreversible photochromic reactions in which colouration/decolouration cycles can be repeated more than 104 times without significant loss of performance.

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Benzothiophene – Wikipedia,
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Transition-Metal-Free Synthesis of 1,2-Disubstituted Indoles

Herein, we report a new transition-metal-free robust and cost-effective method for synthesis of 1,2-disubstituted indoles from easily available unactivated (i.e. without EWG, PPh3 or SiR3 groups) tertiary amides. Scope of synthetic applicability of the presented protocol was shown on 23 examples of 1,2-disubstituted indoles with different substitution patterns obtained in good to excellent yields. The reported method turned out to be especially effective for synthesis of N-arylated 2-CF3-indoles. Moreover, this approach can be performed in a one-pot two-step manner directly from commercially available secondary amines. Mechanistic studies showed that acyl transfer might be an important step in the course of the reaction. Viability of the presented approach for benzofurans and benzothiophenes synthesis was also discussed.

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Benzothiophene – Wikipedia,
Benzothiophene | C8H6S – PubChem

 

Discovery of C9H7BrS

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Convenient synthesis of photochromic symmetrical or unsymmetrical bis(heteroaryl)maleimides via the Suzuki-Miyaura cross-coupling reaction

A general method for the synthesis of symmetrical or unsymmetrical bis(heteroaryl)maleimides by a one-pot procedure involving Suzuki-Miyaura cross-coupling sequence was developed on the basis of the reaction of 3,4-diiodo-1-benzyl-1H-pyrrole-2,5-dione with cyclic boronate esters using PdCl2(dppf) as the catalyst. Photochromic properties of the products were examined.

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New explortion of C9H7BrS

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Dihydropyridines useful in the treatment of angina and stroke

This invention provides certain substituted dihydropyridines, their pharmaceutical formulations, and their use for causing vasodilation in mammals.

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A SYNTHESIS OF BENZONAPHTHO<2,3-d>THIOPHENE DERIVATIVES via BENZOTHIOPHENE-2,3-QUINODIMETHANE INTERMEDIATES

2-Methyl- and 2-ethyl-3-(alpha-aryl)hydroxymethylbenzothiophene (6a)-(6d) were heated at 400 deg C for 5 min to yield the corresponding benzonaphtho<2,3-d>thiophene derivatives (9a)-(9d), respectively.In a similar fashion, the alcohol (8a) gave 5-methylbenzonaphtho<2,3-d>thiophene (9e) and 5,10-dimethyl derivative (3). 8-Methoxy-5-methyl- (9f) and 5-phenyl derivative (9g) were obtained from the corresponding alcohols (8b) and (8c), respectively.

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Reversibly photoswitchable nucleosides: Synthesis and photochromic properties of diarylethene-functionalized 7-deazaadenosine derivatives

Photochromic nucleosides were designed that combine the structural features and molecular recognition properties of nucleic acids with the light-sensitivity of diarylethenes. Target compounds 1a-c consist of a 7-deazaadenosine unit that is linked to a thiophene as the second aryl functionality via a 1,2-cyclopentenyl linker. These nucleoside analogues undergo a reversible electrocyclic rearrangement, generating strongly colored closed-ring isomers upon irradiation with UV-light, while exposure to light in the visible range triggers the cycloreversion to the colorless opened-ring form. UV-vis spectroscopy, HPLC, and 1H NMR measurements revealed recognition of complementary thymidine and up to 97% conversion to the thermally stable closed-ring isomers after illumination with UV-light. The required wavelength for ring closure was found to vary depending on the substituents attached to the thiophene moiety. In a first design step, we used this important feature of diarylethenes to shift the switching wavelength from initially 300 nm (1a) to 405 nm (1cH+). In a second step, we generated a pair of orthogonal switches, differing enough in their respective switching wavelengths to be controlled independently in the same sample. Finally, a molecular switch was developed that showed both photochromism and acidichromism, thereby illustrating the possibility to gate the spectral properties to multiple stimuli. These new photochromic nucleosides represent useful building blocks for the generation of light-sensitive nucleic acids either by inducing conformational changes upon isomerization or by exploring the different spectral properties of the closed and opened isomers, for example, for use as reversible fluorescence quenchers.

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Photoswitchable “turn-on” Fluorescence Diarylethenes: Substituent Effects on Photochemical Properties and Electrochromism

A series of “turn-on” fluorescence diarylethenes derived from 2,3-bis(2-methylbenzo[b]thiophen-3-yl)-5,6-dihydro-4H-thieno[2,3-b]thiopyran-4-one (1) with alkyl and acetyl substituents were synthesized. The photochemical and photophysical properties of these derivatives, including the photoreaction of crystalline 1, were thoroughly investigated to reveal substituent effects on their properties. The results indicated that alkyl substituents did not significantly affect the absorption and emission spectra of the diarylethenes. However, large absorption and emission wavelength shifts were observed for the diarylethene with an acetyl substituent due to extension of pi-pi conjugation. Significantly, all of the fluorescent ring-closed forms of the compounds isomerized to their ring-open forms in the presence of Cu2+ in the dark. EPR results provide clear evidence for the formation of the compound 1 radical cation intermediate that might be generated in the reaction between c-1 and Cu2+. DFT calculations found that the ground-state activation energy for ring-opening of 1.+ was approximately 9.2 kcal mol-1 lower than that of 1 without Cu2+, such that a Cu2+-catalyzed oxidative cycloreversion reaction at room temperature might be possible.

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Substituent effects on the photochromic properties of benzothiophene-based derivatives

Five diarylethene photochromic derivatives, the structures of which incorporate a central benzothiophene unit, a left-hand thiazole group, and a right-hand benzothiophene group, have been prepared. The compound with a thiazole unit with no substituent on the reaction-center carbon atom reveals an unprecedented transformation upon light irradiation. When the 4-position of thiazole is protected by a methyl group, the compounds show high photosensitivity and photochromic properties. In this case, light irradiation affords new compounds with [5]helicene structures featuring the highest redshifted absorption maxima reported to date.

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